CN111889101B - Modified composite oxide catalyst for synergistic purification of VOCs and NO and preparation method thereof - Google Patents
Modified composite oxide catalyst for synergistic purification of VOCs and NO and preparation method thereof Download PDFInfo
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- CN111889101B CN111889101B CN202010813319.1A CN202010813319A CN111889101B CN 111889101 B CN111889101 B CN 111889101B CN 202010813319 A CN202010813319 A CN 202010813319A CN 111889101 B CN111889101 B CN 111889101B
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- 239000002131 composite material Substances 0.000 title claims abstract description 170
- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 49
- 238000000746 purification Methods 0.000 title claims abstract description 14
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003546 flue gas Substances 0.000 claims abstract description 17
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 238000002156 mixing Methods 0.000 claims abstract description 6
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
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- 150000002696 manganese Chemical class 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 230000010718 Oxidation Activity Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
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- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
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- 239000012362 glacial acetic acid Substances 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 150000002823 nitrates Chemical class 0.000 description 2
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- 239000012286 potassium permanganate Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Catalysts (AREA)
Abstract
The invention relates to a modified composite oxide catalyst for synergistic purification of VOCs and NO and a preparation method thereof. The modified composite oxide catalyst is prepared from AMn2O5Wherein A is Sm1‑yOr Sm1‑x‑yMx‑zM is one or more of La, Y, Sr, Ce, Ba, Ca, Gd, Nd and Pr, x is more than 0 and less than 1, Y is not equal to 0, z is not equal to 0, and x is not equal to>z, y and z may be the same or different. The modified composite oxide catalyst is prepared by mixing an unmodified composite oxide AMn in which y and z are both 02O5Modified, and both the modified and unmodified oxide catalysts have a mullite structure. The modified composite oxide of the invention keeps the excellent high temperature resistance of the original composite oxide structure, and can realize the performance of efficiently removing two pollutants of VOCs and NO simultaneously by one catalyst. Therefore, the modified composite oxide catalyst is suitable for the synergistic purification and removal of VOCs and NO in flue gas and motor vehicle tail gas in industries of steel sintering, waste incineration and the like.
Description
Technical Field
The invention belongs to the technical field of air pollution control, and relates to a modified composite oxide catalyst for efficiently and synergistically purifying Volatile Organic Compounds (VOCs) and NO, a preparation method and application thereof, in particular to the cooperative control of the VOCs and the NO, wherein target control pollutants mainly come from smoke in industries such as steel sintering, waste incineration and the like, motor vehicle exhaust and the like.
Background
The emission of smoke and motor vehicle tail gas in industries such as steel sintering, waste incineration and the like causes serious harm to the air quality environment in China. Aiming at the smoke of the industries of steel sintering, waste incineration and the like and the tail gas of motor vehicles, the exhaust gas contains a large amount of pollutants such as particulate matters and SO2Acid gases such as NOx and VOCs. For example, the steel industry, the environmental protection department of 2012 issued emission standards for atmospheric pollutants in the steel sintering and pelletizing industry (GB28662-2012), and the main pollutants produced by sintering equipment respectively implement 50mg/m of particles3、SO2 200mg/m3、NOx 300mg/m3，CO 5000mg/m3The limit criteria of (2). Among them, CO is a reducing gas widely present in steel sintering, waste incineration fumes, and automobile exhaust. NO in the atmospherexThe interaction between sulfur oxide and VOCs results in the conversion of primary particulate matter to secondary particulate matter pollutants in the atmosphere, and then results in haze weather. Therefore, the control of the emission of VOCs and NO has important significance for improving the air quality in China. The catalyst capable of efficiently removing VOCs and NO at the same time is urgently needed to be developed, VOCs and NO are converted into non-toxic compounds, and the catalyst is a new technology with good application prospect.
The catalytic oxidation technology is a typical gas-solid phase catalytic reactionShould be used. In the environmental field, the pollutants (VOCs, NO and the like) are deeply oxidized by active oxygen. The catalytic oxidation of VOCs or NO takes place on the surface of solid catalyst, VOCs or NO molecules are enriched on the surface of catalyst by adsorption, the reaction rate is increased by reducing the reaction activation energy of catalyst, VOCs are oxidized into CO2And oxidizing NO into nitrate and adsorbing the nitrate on the surface of the catalyst, and reducing the nitrate adsorbed on the surface of the catalyst into nitrogen by utilizing reducing gas such as CO in the flue gas.
Noble metal catalysts generally have higher catalytic activity than transition metal composite oxides, but are costly and have low thermal stability. Composite oxide catalyst (manganese-based mullite with structural formula of AMn2O5) The composite oxide has excellent oxidation performance and extremely high thermal stability, is a material with high-efficiency catalytic activity on the catalytic oxidation of VOCs or NO, and becomes a mixed oxide system which is researched more in the field of heterogeneous catalysis at present.
Citation 1 discloses a mullite-type composite oxide catalyst for nitric oxide oxidation, which has a general chemical formula A1-xA'xB'yO5Wherein A and A' are each independently one of rare earth metal or alkaline earth metal element, the rare earth metal element can be La, Ce, Nd, Gd and Sm, and the alkaline earth metal element can be Mg, Ca, Sr and Ba; b and B' are each independently a transition metal element, which may be Fe, Co, Mn, Ni, Ti, and Cr. In addition, citation 1 studies the catalytic performance of the mullite-type composite oxide catalyst on nitric oxide, and proves that the mullite-type composite oxide catalyst and Pt/γ -Al2O3Compared with the nitric oxide conversion rate, the conversion rate is obviously improved.
Citation 2 discloses a general formula AM2O5-xThe compound is applied as a catalyst for catalyzing VOC combustion, wherein A can be selected from one or more of La, Ce, Pr, Nd, Pm, Sm, … Bi and Y, M can be selected from one or more of Ti, V, Cr, Mn, Fe and the like, and x is between 0 and 1. Also, cited document 2 utilizes the general formula AM2O5-xThe compound catalyzes the VOC combustion to prove that the mullite composite oxide has large VOCPart of the components can play a good catalytic effect.
In addition, in order to improve the catalytic activity, modified manganese-based mullite and a manganese-based mullite composite have been studied. For example, cited reference 3 discloses Ag-modified manganese-based mullite, and cited reference 4 discloses a manganese-based mullite/nitrogen-doped graphene composite oxygen electrocatalyst.
Although the above catalysts all have been able to increase the activity of the manganese-based mullite catalyst to some extent, there is still room for further improvement. Moreover, none of these references investigated the synergistic purification of VOCs and NO by manganese-based mullite catalysts.
Cited documents:
cited document 1: CN104624184A
Cited document 2: CN110433794A
Cited document 3: CN110013849A
Cited document 4: CN109289892A
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a modified composite oxide catalyst with more Mn active sites. The modified composite oxide catalyst can be used for purifying flue gas, has the advantages of low ignition temperature, high conversion efficiency, good high temperature resistance, excellent water resistance, low price and the like, and can be used for catalytic combustion reaction of VOCs, oxidation reaction of NO and synergistic removal of VOCs and NO. The flue gas in the invention is flue gas generated in industries of steel sintering, waste incineration and the like and motor vehicle tail gas.
The invention also aims to provide a preparation method and application of the catalyst.
Means for solving the problems
After long-term intensive research by the inventors, it is found that the technical problems can be solved by implementing the following technical scheme:
1. a modified composite oxide catalyst, characterized in that the modified composite oxide catalyst is represented by the following formula:
AMn2O5
wherein A is Sm1-yOr Sm1-x-yMx-zM is one or more of La, Y, Sr, Ce, Ba, Ca, Gd, Nd and Pr, x is more than 0 and less than 1, Y is not equal to 0, z is not equal to 0, and x is not equal to>z, y and z are the same as or different from each other,
the modified composite oxide catalyst is prepared by mixing an unmodified composite oxide AMn in which y and z are both 02O5Is obtained by modification, and the modified starch is obtained,
the modified composite oxide catalyst and the unmodified oxide catalyst both have mullite structures.
2. The modified composite oxide catalyst according to 1, wherein y is in the range of 0.01 to 0.1 and z is in the range of 0.001 to 0.1.
3. The modified composite oxide catalyst according to the above 1 or 2, wherein the modified composite oxide catalyst has a BET specific surface area of 11 to 30m2(ii)/g, the average pore diameter is 30 to 60 nm.
4. The modified composite oxide catalyst according to any one of above 1 to 3, wherein in the catalyst amount: 0.1g, particle size: 40-60 meshes, flue gas concentration: NO 500ppm, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1Under the experimental conditions of (a) and (b),
t of the modified composite oxide catalyst80-NOAt a temperature below 320 ℃, wherein T80-NOIs the temperature at which the NO conversion is 80%.
5. The modified composite oxide catalyst according to any one of above 1 to 3, wherein in the catalyst amount: 0.1g, particle size: 40-60 meshes, flue gas concentration: toluene 100ppm, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1Under the experimental conditions of (a) and (b),
t of the modified composite oxide catalyst80-tolueneBelow 290 ℃ in which T80-tolueneIs the temperature at which the toluene conversion is 80%.
6. According to any of the above 1-3The modified composite oxide catalyst, wherein the ratio of the catalyst amount: 0.1g, particle size: 40-60 meshes, flue gas concentration: NO 500ppm, toluene 100ppm, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1Under the experimental conditions of (a) and (b),
t of the modified composite oxide catalyst80-NOAt a temperature below 325 ℃, T80-tolueneBelow 290 ℃ in which T80-NOIs the temperature at which the NO conversion is 80%, T80-tolueneIs the temperature at which the toluene conversion is 80%.
7. A method for producing the modified composite oxide catalyst according to the above 1, characterized by comprising the steps of:
an unmodified composite oxide AMn in which y and z are both 02O5Etching in an acid solution at a temperature of 18 ℃ to 25 ℃ to obtain a compound represented by formula AMn2O5The modified composite oxide catalyst shown in the above formula,
wherein A is as defined in 1 above.
8. The method of 7 above, wherein the acid solution is selected from one or more of solutions of nitric acid, acetic acid, hydrochloric acid, phosphoric acid, sulfuric acid, and potassium permanganate.
9. The method according to 7 or 8 above, wherein the unmodified composite oxide AMn in which y and z are both 02O5The metal salt of A and the metal salt of Mn are mixed according to the molar ratio of A to Mn of 1: 1.8-1: 2.2, and the mixture is prepared according to a sol-gel method or a coprecipitation method.
10. Use of a modified composite oxide catalyst according to any one of the above 1-6 for catalytic purification or co-purification removal of VOCs or NO.
ADVANTAGEOUS EFFECTS OF INVENTION
Through the implementation of the technical scheme, the invention can obtain the following technical effects:
(1) the modified composite oxide catalyst of the invention is prepared from an unmodified composite oxide AMn2O5(y and z are both 0) structureSelectively etching partial ions at the A site of the structural unit, effectively improving the oxygen vacancy content of the catalyst, exposing more Mn active sites with catalytic activity, and improving the surface Mn of the Mn active sites4+/Mn3+The species proportion enriches active oxygen species on the surface of the catalyst, so that the prepared modified composite oxide not only retains the excellent high-temperature resistance of the original composite oxide, but also obviously improves the catalytic oxidation activity of VOCs and NO.
(2) Modified composite oxide catalyst AMn prepared by the invention2O5(y and z are not 0) in comparison with the unmodified complex oxide AMn2O5(y and z are both 0) the temperature required for reaching the same catalytic activity is reduced, energy is saved and consumption is reduced.
(3) The invention has simple modification process, low operation cost, easy industrial application and higher market promotion prospect.
Drawings
FIG. 1 is an unmodified composite oxide SmMn prepared in example 12O5(hereinafter referred to simply as "SMO") and a modified composite oxide SMO-H.
FIG. 2 is a Transmission Electron Microscope (TEM) image of SMO and SMO-H prepared in example 1, where (a) to (c) are TEM images of SMO and (d) to (f) are TEM images of SMO-H; (g) TEM-Mapping images of SMO (H) and TEM-Mapping images of SMO-H (i) to (j).
FIG. 3 is a graph showing NO conversion of SMO and SMO-H.
FIG. 4 is a graph showing toluene conversion for SMO (FIG. 4a) and SMO-H (FIG. 4b) catalysts.
Fig. 5 is a graph showing the conversion of the SMO-H catalyst for the co-purification of both NO and toluene.
FIG. 6 shows a modified composite oxide catalyst Sm0.8-yCe0.2-zMn2O5(y and z are not both 0) in terms of NO conversion.
FIG. 7 shows a modified composite oxide catalyst Sm0.8-yCe0.2-zMn2O5(y and z are not both 0) in terms of toluene conversion.
FIG. 8 shows a modified complex oxideCatalyst Sm0.8-yCe0.2-zMn2O5(y and z are not both 0) in the presence of toluene and NO.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the term "optional" or "optional" is used to indicate that certain substances, components, performance steps, application conditions, and the like are used or not used.
In the specification, the unit names used are all international standard unit names.
In the present specification, the term "plurality" means two or more than two unless otherwise specified.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< first aspect >
A first aspect of the present invention provides a novel modified composite oxide catalyst. The modified composite oxide catalyst has more Mn active sites, and can greatly improve the cooperative catalytic capability of VOCs and NO.
Catalyst composition
The modified complex oxide catalyst of the present invention may be represented by formula AMn2O5Wherein A is Sm1-yOr Sm1-x-yMx-zM is one or more of La, Y, Sr, Ce, Ba, Ca, Gd, Nd and Pr, x is more than 0 and less than 1, Y is not equal to 0, z is not equal to 0, and x is not equal to>z, y and z are the same or different from each other.
The modified composite oxide catalyst of the invention is obtained by subjecting an unmodified composite oxide AMn in which y and z are both 0 to catalytic action2O5And the modified composite oxide catalyst and the unmodified oxide catalyst both have a mullite structure.
According to the studies by the present inventors, it was found that the value of x in the modified composite oxide of the present invention is in the range of more than 0 and less than 1, preferably in the range of more than 0 and 0.5 or less, and more preferably in the range of more than 0 and 0.2 or less. The value of y is preferably in the range of 0.01 to 0.1, more preferably in the range of 0.02 to 0.08, and still more preferably in the range of 0.02 to 0.05. The value of z is preferably in the range of 0.001 to 0.1, more preferably in the range of 0.002 to 0.08, and still more preferably in the range of 0.002 to 0.06. When the values of y and z are within this range, the modified catalyst has a greater improvement in catalytic ability to VOCs and NO than the pre-modified catalyst.
In addition, the M element in the modified composite oxide of the present invention may be one or more selected from La, Y, Sr, Ce, Ba, Ca, Gd, Nd, and Pr. When M is two or more of the above elements, the element ratio therebetween is not particularly limited, and compounding may be performed as necessary.
In some preferred embodiments of the present invention, M is preferably Sr and Ce from the viewpoint of catalytic performance and ease of preparation.
Other ingredients
In some preferred embodiments of the present invention, no other metal elements other than element a and element Mn may be substantially included in the catalyst of the present invention. By "not substantially included" in the context of the present invention is meant that the materials or components comprising the materials are not introduced as raw materials in forming or making the catalysts of the present invention.
In other specific embodiments, other metal elements may be added as necessary in addition to the above-mentioned components of the catalyst of the present invention without affecting the technical effect of the present invention. Other metallic elements that may be used include one or more of tungsten, copper, nickel, and rare earth elements. And the total content of these additional metal elements is 1 mol% or less, preferably 0.8 mol% or less, for example 0.2 mol% or less, based on the total number of moles of metal elements in the catalyst.
Further, the catalyst of the present invention may be a supported catalyst or an unsupported catalyst. The carrier is not particularly limited and may be a carrier commonly used in the art, such as cordierite, a metal oxide carrier (e.g., alumina, titania, etc.), carbon black, a molecular sieve, hydrotalcite, natural zeolite, ash in a fluidized bed, etc., and a typical carrier may be one of cordierite, alumina, a molecular sieve, or hydrotalcite.
Catalyst crystal structure
As described above, the modified composite oxide catalyst of the invention is obtained by subjecting an unmodified composite oxide AMn in which y and z are both 0 to catalytic oxidation2O5And y is preferably in the range of 0.01 to 0.1, and z is preferably in the range of 0.001 to 0.1, both of which are small values, and thus do not cause a change in crystal structure. Therefore, both the modified composite oxide catalyst and the unmodified oxide catalyst of the present invention have a mullite structure.
The following description will specifically take A as Sm.
FIG. 1 shows an unmodified composite oxide SmMn prepared in example 12O5(hereinafter referred to as "SMO"), XRD pattern of modified composite oxide catalyst SMO-H obtained by acid etching at room temperature.
As can be seen in FIG. 1, the diffraction peaks and SmMn of the unmodified SMO2O5Standard card (JCPDS No.52-1096) was in agreement, indicating good crystallinity of the unmodified SMO. The XRD pattern of the modified composite oxide catalyst SMO-H obtained at room temperature was not significantly changed from that of the unmodified SMO, indicating that the product obtained by acid etching at room temperature was still of mullite structure.
The inventors of the present invention carried out ICP measurement of the unmodified composite oxide SMO and the modified composite oxide catalyst SMO — H, and found that y was 0.02 by calculation (see table 1 in example 1 described later), which indicates that the amount of Sm element dissolved by acid etching at room temperature was small.
Morphology and specific surface area
The changes in morphology, specific surface area and surface element composition of the modified composite oxide catalyst during acid treatment are described below by taking the case where A is Sm as an example.
As can be seen from comparison of (a), (b), and (d) and (e) in fig. 2, the unmodified composite oxide SMO and the modified composite oxide SMO — H are each a nanorod. Therefore, modification by acid etching at room temperature has substantially no influence on the morphology of the composite oxide.
The BET nitrogen adsorption specific surface area measurements were made on the unmodified composite oxide SMO and the modified composite oxide SMO-H, respectively, and the results showed that the pore diameter of the modified composite oxide SMO-H was slightly decreased and the specific surface area and pore volume were slightly increased as compared with the unmodified composite oxide SMO. From this, it is also known that the bulk structure of the composite oxide catalyst does not change much before and after the acid etching.
Variations in surface structure
At AMn2O5In the structure, the A-site ion mainly acts to stabilize the structure of the composite oxide and can control the valence state and the dispersion state of the Mn element. In addition, AMn2O5The catalytic performance is due to the octahedral field (MnO)6) And vertebral body field (MnO)5) Two types of crystal field structures form a special Mn-Mn dimer active site. Selective removal of structural units using an etching solutionThe ions at the A site can effectively improve the oxygen vacancy content on the surface of the catalyst, expose more Mn active sites with catalytic activity and improve the Mn on the surface of the catalyst4+/Mn3+The species proportion enriches the active oxygen species on the surface of the catalyst, and the catalytic oxidation performance of VOCs and NO is greatly improved. A series of modified composite oxide catalysts with different molar ratios can be obtained by regulating and controlling the etching degree, and the result shows that the modified composite oxide catalyst obtained by etching has more excellent catalytic oxidation performance and thermal stability of VOCs and NO.
The results of ICP, XPS, TEM-EDS and TEM-Mapping tests on the modified composite oxide catalyst SMO-H show that Sm and Mn are slightly soluble but Sm is more soluble than Mn when acid etching is carried out at room temperature, which is the key to making oxygen vacancies. As can be confirmed by the above tests, the surface MnO of the resulting catalyst6The octahedral structure is increased to form a specific Mn — Mn dimer active site, which is a main active site of NO oxidation reaction, thus promoting NO oxidation activity. While an increase in the surface Mn valence and an increase in oxygen vacancies are critical to the increase in the oxidation reaction of VOCs. Therefore, the modified composite oxide of the invention not only can catalyze the catalytic combustion reaction of VOCs and the oxidation reaction of NO, but also can synergistically purify both VOCs and NO.
In addition, water affects the catalytic performance of the catalyst, and the catalyst of the present invention has excellent water resistance.
< second aspect >
A second aspect of the present invention provides a method for producing a modified composite oxide catalyst, which is the same as the modified composite oxide catalyst described or defined in < first aspect > above.
In some specific embodiments, the preparation method of the present invention comprises: an acid etching step and a washing and drying step. Optionally, the production method of the present invention further includes a step of producing an unmodified composite oxide.
Step of preparing unmodified complex oxide
The method for producing the unmodified composite oxide of the present invention is not particularly limited, and can be produced using production methods known in the art, such as hydrothermal synthesis, coprecipitation, sol-gel method, and the like, as long as the crystal structure, average pore diameter, BET specific surface area, and the like of the produced unmodified composite oxide are within the above-described ranges of the present invention.
Therefore, the unmodified composite oxide AMn in the invention2O5The preparation method of (1) comprises the step of mixing the soluble A salt and the soluble manganese salt. Thereafter, the mixture including the two salts may be subjected to further steps such as hydrothermal treatment, coprecipitation, or formation of a solvent gel, thereby obtaining an unmodified composite oxide AMn2O5。
The following description will be made by taking a sol-gel method as an example.
Preparation of unmodified Complex oxide AMn by Sol-gel method2O5The method mainly comprises the following steps:
preparing a mixed solution of soluble A salt and soluble manganese salt according to a molar ratio; adding a complexing agent; heating the mixed solution to form a sol; then drying and roasting are carried out.
In an embodiment of the invention, A is Sm1-yOr Sm1-x-yMx-zM is one or more of La, Y, Sr, Ce, Ba, Ca, Gd, Nd and Pr, x is more than 0 and less than 1, Y is not equal to 0, z is not equal to 0, and x is not equal to>z, y and z are the same or different from each other.
In the unmodified composite oxide of the present invention, y and z are both 0.
According to the studies by the present inventors, it has been found that in the modified composite oxide of the present invention, the value of y is preferably in the range of 0.01 to 0.1, and the value of z is preferably in the range of 0.001 to 0.1. When the values of y and z are within this range, the modified catalyst has a greater improvement in catalytic ability to VOCs and NO than the pre-modified catalyst.
In addition, the M element in the modified composite oxide of the present invention may be one or more selected from La, Y, Sr, Ce, Ba, Ca, Gd, Nd, and Pr. When M is two or more of the above elements, the element ratio therebetween is not particularly limited, and compounding may be performed as necessary.
In some preferred embodiments of the present invention, M is preferably Sr and Ce from the viewpoint of catalytic performance and ease of preparation.
When A is Sm1-x-yMx-zIn the case of the compound, the molar ratio of the soluble salt of Sm to the soluble salt of M is 1-x-y: x-z. The Sm salt and the M salt may be their nitrates or chlorides, with the nitrates preferably being used from the viewpoint of ready availability of the product.
In some embodiments of the invention, a complexing agent may be added in order to mix the metal ions uniformly. Examples of complexing agents include citric acid and the like.
When the gel is formed by heating, the heating is preferably carried out in a water bath, and the heating temperature can be 40-80 ℃, and preferably 50-60 ℃.
The drying method is not particularly limited, and the product may be dried in an atmospheric environment using equipment generally used in the art. The drying temperature can be 80-150 ℃ in some embodiments, and is preferably 100-120 ℃; the drying time is not limited, and may be, for example, 8 to 24 hours, preferably 10 to 18 hours, and more preferably 12 to 15 hours.
The method of calcination is not particularly limited, and the product can be calcined in an atmospheric environment using equipment that is usual in the art. The roasting temperature can be 400-900 ℃, preferably 500-800 ℃. The roasting time can be 8-15 h, preferably 10-12 h.
Acid etching step
The step of acid-etching the unmodified composite oxide obtained by the above step includes: immersing the unmodified composite oxide in an acid solution to perform acid etching at a temperature of 18 ℃ to 25 ℃ (room temperature), thereby obtaining a modified composite oxide represented by formula AMn2O5The modified complex oxide catalyst shown. Wherein A is as defined above.
In an embodiment of the invention, the acid solution is one or more of a nitric acid, glacial acetic acid, hydrochloric acid, sulfuric acid and potassium permanganate solution. Among them, nitric acid is more preferably used. The concentration of the acid solution is not particularly limited, and may be 1M to 10M, preferably 3M to 10M, and more preferably 5M to 10M in the embodiment of the present invention.
In an embodiment of the present invention, the temperature of the acid etching is room temperature, and is generally in the range of 18 to 25 ℃. By mixing unmodified AMn2O5The mullite composite oxide is subjected to acid etching at room temperature to remove a small amount of A site elements, so that more Mn active sites with catalytic activity can be exposed, and Mn on the surface can be obtained4+/Mn3+Enhanced, thus modified AMn2O5The composite oxide catalyst of type (iii) can be advantageously used for the synergistic purification of VOCs and NO.
In the embodiment of the present invention, the acid etching time may be 6 to 15 hours, preferably 8 to 12 hours, and more preferably 9 to 10 hours.
Washing and drying step
And (3) centrifugally separating the solution subjected to acid etching, washing the solution with deionized water until the solution is neutral, and drying the product to obtain the modified composite oxide catalyst.
In the embodiment of the invention, the drying temperature is 80-150 ℃, preferably 90-120 ℃, and more preferably 100-120 ℃. The drying time is 5-18 h, preferably 8-12 h.
< third aspect >
In a third aspect of the invention, there is provided the use of the above-described modified composite oxide catalyst for the purification of VOCs, NO or both VOCs and NO. The VOCs are not particularly limited, and may include generally-referred VOCs, and specifically may include hydrocarbons (alkanes, alkenes, alkynes, cyclic hydrocarbons, aromatic hydrocarbons), ketones, esters, alcohols, ethers, aldehydes, acids, amines, nitriles, epoxy compounds, and the like.
As described above, in the present invention, the manganese-based mullite AMn is prepared by subjecting manganese-based mullite2O5In the modified composite oxide catalyst obtained by performing acid etching on the composite oxide with the structure at room temperature and dissolving A site element in a small amount, the number of oxygen vacancies after etching is increased, the average valence of Mn is increased, and MnO on the surface is MnO6The octahedral structure is increased, so that a specific Mn-Mn bi-component is formedA polymer active site. Therefore, the modified composite oxide of the invention not only can catalyze the catalytic combustion reaction of VOCs and the oxidation reaction of NO, but also can synergistically purify both VOCs and NO.
The conditions for the catalytic performance test are not particularly limited, and test conditions common in the art may be used. In some specific embodiments, the test conditions and resulting catalytic performance are as follows.
When the smoke is NO, the experimental conditions are as follows:
the dosage of the catalyst is as follows: 0.1g, particle size: 40-60 meshes, flue gas concentration: NO 500ppm, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1，
T of modified composite oxide catalyst80-NOAt a temperature below 320 ℃, wherein T80-NOIs the temperature at which the NO conversion is 80%.
When the flue gas is toluene, the experimental conditions are as follows:
the catalyst dosage is as follows: 0.1g, particle size: 40-60 meshes, flue gas concentration: toluene 100ppm, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1，
T of modified composite oxide catalyst80-tolueneBelow 290 ℃ in which T80-tolueneIs the temperature at which the toluene conversion is 80%.
When the flue gas is both NO and toluene, the experimental conditions are:
the dosage of the catalyst is as follows: 0.1g, particle size: 40-60 meshes, flue gas concentration: 500ppm of NO, 100ppm of toluene, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1，
T of modified composite oxide catalyst80-NOAt a temperature below 325 ℃, T80-tolueneBelow 290 ℃ in which T80-NOIs the temperature at which the NO conversion is 80%, T80-tolueneIs the temperature at which the toluene conversion is 80%.
Examples
The present invention will be described below with reference to specific examples.
First, the structure and performance characterization of the catalyst will be explained.
(1) Crystal structure
The XRD data of all samples in the present invention were tested on a Rigaku X-ray diffractometer with a Cu ka radiation source (λ ═ 0.15405nm) at a voltage of 40kV and a current of 200 mA.
(2) BET specific surface area test
The BET specific surface area was obtained by nitrogen adsorption-desorption on a Quantachrome Autosorb-1MP apparatus at a liquid nitrogen temperature (-196 ℃ C.).
(3) Topography testing
TEM images, TEM-EDS and TEM-Mapping were taken by using a transmission electron microscope (JOEL, Japan) at an acceleration voltage of 200 kV.
(4) ICP test
Inductively coupled plasma spectroscopy (ICP-AES) (OPTIMA5300DV) by PE was used to determine the content of the different elements in the catalyst.
(5) XPS test
Information on surface elements and valence states was obtained using a K-Alpha type X-ray photoelectron spectrometer manufactured by Thermo Fisher, USA. The excitation source was an Mg target, and the Binding Energy (BE) of each element on the surface was corrected by the binding energy (284.6eV) of C1 s.
(6) Test for catalytic Performance
The catalytic performance test steps of the invention are as follows:
the catalytic oxidation reaction was carried out in a continuous-flow microreactor made from quartz tubes (id ═ 6 mm). Reaction mixture (500ppm NO or 100ppm toluene or both + 20% O2+N2(remainder)) the total flow rate was 100mL min-1GHSV of 60,000mL g-1h-1. Concentrations of reactants and products were determined by Antaris, available from Thermo Fisher Scientific IncTMAnd (5) carrying out online monitoring on the IGS gas analyzer. The conversion (X) was calculated according to the following formulaNO,XToluene，％)。
Wherein, CinAnd CoutConcentrations of NO and toluene corresponding to the inlet and outlet, respectively.
Example 1
(1) Unmodified composite oxide SmMn2O5Preparation of (SMO)
0.1mol of Sm (NO)3)3·6H2O、0.2mol Mn(NO3)20.3mol of citric acid was mixed in a beaker, and 1L of deionized water was added. Steaming in water bath at 60 deg.C to obtain sol, air drying, and drying at 120 deg.C for 12 hr. Then, the mixture was calcined at 500 ℃ and 800 ℃ for 10 hours, respectively. Thus, an unmodified composite oxide SmMn was obtained2O5(SMO)。
(2) Modified composite oxide Sm1-yMn2O5Preparation of (SMO-H)
SmMn prepared in the above (1) was reacted at room temperature2O5Soaking in 5M HNO3The solution was kept for 10 h. Centrifugally separating the modified composite metal oxide after acid etching, washing the modified composite metal oxide to be neutral by deionized water, and then drying the modified composite metal oxide in a drying oven at 120 ℃ for 12 hours to obtain the modified composite oxide catalyst Sm1-yMn2O5(y≠0)(SMO-H)。
As can be seen from fig. 1, the XRD pattern of the modified composite oxide catalyst SMO-H was not significantly changed compared to that of the unmodified SMO, indicating that the crystal structure of the modified product obtained after acid etching was not significantly changed.
In addition, as can be seen from comparison of (a), (b) with (d) and (e) in fig. 2, the unmodified composite oxide SMO and the modified composite oxide SMO — H are each a nano-stub. Therefore, the morphology of the composite oxide is not substantially affected by acid etching at room temperature.
The BET nitrogen adsorption specific surface area measurement was performed on the unmodified composite oxide SMO and the modified composite oxides SMO — H, respectively, and the results are shown in table 1 below. The results show that the pore diameter of the modified composite oxide SMO — H is slightly reduced and the specific surface area and pore volume are slightly increased as compared with the unmodified composite oxide SMO.
The test results show that the bulk structure of the composite oxide catalyst does not change much before and after acid etching.
TABLE 1 ICP and BET data for SMO and SMO-H
ICP measurements were performed for SMO and SMO-H, and the results are shown in Table 1. As is clear from Table 1, the amount of Sm was slightly reduced after acid etching. Can be calculated to obtain Sm1-yMn2O5Y in (2) is 0.02.
In addition, XPS, TEM-EDS and TEM-Mapping tests were performed on SMO and SMO-H. The XPS and TEM-EDS results are shown in Table 2. The TEM-Mapping test results are shown in FIG. 2. In which FIGS. 2(g) and (H) are diagrams of SMO, and FIGS. 2(i) and (j) are diagrams of SMO-H.
TABLE 2 surface element composition from XPS and EDS results for SMO and SMO-H
As shown in Table 2, from the results of XPS and EDS, Mn in the surface of SMO-H which is the product after etching is observed4+/Mn3+And Olatt/OadsAre greatly improved, which shows that the oxygen vacancy on the surface is increased after acid etching, and the surface MnO of the obtained catalyst is MnO6The octahedron structure is increased, a special Mn-Mn dimer active site is formed, and the surface Mn valence state is improved. While an increase in the surface Mn valence and an increase in oxygen vacancies are critical to the increase in VOCs and NO oxidation.
In order to examine the catalytic performance of the modified composite oxide catalyst SMO-H and the unmodified composite oxide SMO, the catalytic performance of VOCs, NO, and both were respectively tested using them. The results are shown in FIGS. 3 to 5.
As is clear from fig. 3 and 4, the modified composite oxide catalyst SMO-H has improved catalytic performance for both NO and VOCs as compared with the unmodified composite oxide catalyst SMO.
More specifically, as can be seen from fig. 3, the unmodified composite oxide catalyst SMO only enabled NO conversion to be as high as 55%, and the temperature at this time was as high as 415 ℃; the modified composite oxide catalyst SMO-H can ensure that the NO conversion rate reaches 80 percent at most and the temperature T is higher80-NOOnly 320 deg.c. The above-mentioned effects of the modified composite oxide catalyst SMO-H are very surprising.
As shown in fig. 4, the modified composite oxide catalyst SMO — H has slightly better catalytic performance for toluene than the unmodified composite oxide catalyst SMO. The temperature at which the conversion of toluene by the unmodified composite oxide catalyst SMO reached 80% was about 300 ℃ (FIG. 4(a)), and the temperature T at which the conversion of toluene by the modified composite oxide catalyst SMO-H reached 80%80-tolueneIs about 290 deg.c (fig. 4 (b)).
The synergistic purification effect of the modified composite oxide catalyst SMO — H on both NO and toluene is shown in fig. 5. As shown in fig. 5, the temperatures at which the modified composite oxide catalyst SMO — H reached 80% conversion of NO and toluene were 325 ℃ and 290 ℃, respectively.
The test result of the catalytic performance shows that the catalytic performance of the modified composite oxide catalyst SMO-H is superior to that of the unmodified composite oxide catalyst SMO, and the modified composite oxide catalyst SMO-H not only can catalyze the catalytic combustion reaction of VOCs and the oxidation reaction of NO, but also can synergistically purify both VOCs and NO.
Example 2
(1) Unmodified composite oxide SmCeMn2O5Preparation of (SCMO)
0.08mol of Sm (NO)3)3·6H2O、0.02mol Ce(NO3)3.6H2O、0.2mol Mn(NO3)20.3mol of citric acid was mixed in a beaker, and 1L of deionized water was added. Steaming in 60 deg.C water bath to obtain sol, taking out, air drying, and drying at 120 deg.C for 12 hr. Then, the mixture was calcined at 500 ℃ and 800 ℃ for 10 hours, respectively. Thus, an unmodified composite oxide SmCeMn was obtained2O5(SCMO)。
(2)Modified composite oxide Sm0.8-yCe0.2-zMn2O5Preparation of (SCMO-H)
SmCeMn prepared in the above (1) was reacted at room temperature2O5(SCMO) was soaked in 3M glacial acetic acid for 10 h. Centrifugally separating the modified composite metal oxide after acid etching, washing the modified composite metal oxide to be neutral by deionized water, and then drying the modified composite metal oxide in a drying oven at 120 ℃ for 12 hours to obtain the modified composite oxide catalyst Sm0.8-yCe0.2-zMn2O5(SCMO-H), wherein y is 0.01, and z is 0.002.
The catalytic performance tests were performed on VOCs, NO and both with SCMO-H catalysts, and the results are shown in FIGS. 6-8.
As shown in FIGS. 6 to 8, the modified SCMO-H catalyst was found to have excellent catalytic effects on NO, toluene and both. Specifically, as shown in fig. 6, the modified SCMO-H catalyst can achieve NO conversions as high as 90% and temperatures of only about 325 ℃. Temperature T when NO conversion reaches 80%80-NOOnly about 280 c. As can be seen from FIG. 7, the temperature T at which the toluene conversion reached 80%80-tolueneOnly about 265 deg.c. As can be seen from fig. 8, the modified SCMO-H catalyst can synergistically purify both NO and toluene. Temperature T when NO conversion reaches 80%80-NOAbout 325 ℃, temperature T when the toluene conversion reaches 80%80-tolueneIs about 280 deg.c.
Example 3
(1) Unmodified composite oxide SmSrMn2O5Preparation of (SSMO)
0.08mol of Sm (NO)3)3·6H2O、0.02mol Sr(NO3)2、0.2mol Mn(NO3)20.3mol of citric acid was mixed in a beaker, and 1L of deionized water was added. Steaming in 60 deg.C water bath to obtain sol, taking out, air drying, and drying at 120 deg.C for 12 hr. Then, the mixture was calcined at 500 ℃ and 800 ℃ for 10 hours, respectively. Thus, an unmodified composite oxide SmSrMn was obtained2O5(SSMO)。
(2) Modified composite oxide Sm0.8-ySr0.2-zMn2O5Preparation of (SSMO-H)
SmSrMn prepared in the above (1) was mixed at room temperature2O5(SSMO) was soaked in 10M nitric acid solution for 10 h. Centrifugally separating the modified composite metal oxide after acid etching, washing the modified composite metal oxide to be neutral by deionized water, and then drying the modified composite metal oxide in a drying oven at 120 ℃ for 12 hours to obtain the modified composite oxide catalyst Sm0.8-ySr0.2-zMn2O5(SSMO-H), wherein y is 0.05 and z is 0.06.
Industrial applicability
The modified composite metal oxide catalyst can be industrially prepared and can be used for the synergistic purification and removal of VOCs and NO in flue gas and motor vehicle tail gas in industries such as steel sintering, waste incineration and the like.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (11)
1. A modified composite oxide catalyst, characterized in that the modified composite oxide catalyst is represented by the following formula:
AMn2O5
wherein A is Sm1-yOr Sm1-x-yMx-zM is one or more of La, Y, Sr, Ce, Ba, Ca, Gd, Nd and Pr, x is more than 0 and less than 1, Y is not equal to 0, z is not equal to 0, and x is not equal to>z, y and z are the same as or different from each other,
the modified composite oxide catalyst is prepared by mixing an unmodified composite oxide AMn in which y and z are both 02O5Is obtained by modification, and the modified starch is obtained,
the modified composite oxide catalyst and the unmodified oxide catalyst both have mullite structures,
wherein y is in the range of 0.01 to 0.1, z is in the range of 0.001 to 0.1,
the modified composite oxide catalyst is prepared by a method comprising the steps of:
an unmodified composite oxide AMn in which y and z are both 02O5Etching in 3M-10M acid solution at 18-25 ℃ for 6-15 hours to obtain a compound represented by the formula AMn2O5The modified complex oxide catalyst shown.
2. The modified composite oxide catalyst according to claim 1, wherein the modified composite oxide catalyst has a BET specific surface area of 11 to 30 m/g and an average pore diameter of 30 to 60 nm.
3. The modified composite oxide catalyst according to claim 1 or 2, wherein the molar ratio of the catalyst used: 0.1g, particle size: 40-60 meshes, flue gas concentration: NO 500ppm, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1Under the experimental conditions of (a) and (b),
t of the modified composite oxide catalyst80-NOAt a temperature below 320 ℃, wherein T80-NOIs the temperature at which the NO conversion is 80%.
4. The modified composite oxide catalyst according to claim 1 or 2, wherein the molar ratio of the catalyst used: 0.1g, particle size: 40-60 meshes, flue gas concentration: toluene 100ppm, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1Under the experimental conditions of (a) and (b),
t of the modified composite oxide catalyst80-tolueneBelow 290 ℃ in which T80-tolueneIs the temperature at which the toluene conversion is 80%.
5. The modified composite oxide catalyst according to claim 1 or 2, wherein the molar ratio of the catalyst used: 0.1g, particle size: 40-60 meshes, flue gas concentration: NO 500ppm, toluene 100ppm, O2Concentration: 10vol.%, N2: balance, total gas amount: 100mL min-1And airspeed: 120000h-1Under the experimental conditions of (a) and (b),
t of the modified composite oxide catalyst80-NOAt a temperature below 325 ℃, T80-tolueneThe temperature of the mixture is below 290 ℃ and,
wherein T is80-NOIs the temperature at which the NO conversion is 80%, T80-tolueneIs the temperature at which the toluene conversion is 80%.
6. The modified composite oxide catalyst according to claim 1, wherein the acid solution is selected from one or more of solutions of nitric acid, acetic acid, hydrochloric acid, phosphoric acid, and sulfuric acid.
7. The modified composite oxide catalyst according to claim 1, wherein the unmodified composite oxide AMn in which y and z are both 02O5The metal salt of A and the metal salt of Mn are mixed according to the molar ratio of A to Mn of 1: 1.8-1: 2.2, and the mixture is prepared according to a sol-gel method or a coprecipitation method.
8. A method for producing the modified composite oxide catalyst according to claim 1, characterized by comprising the steps of:
an unmodified composite oxide AMn in which y and z are both 02O5Etching in 3M-10M acid solution at 18-25 ℃ for 6-15 hours to obtain a compound represented by the formula AMn2O5The modified composite oxide catalyst shown in the above formula,
wherein A is as defined in claim 1.
9. The method of claim 8, wherein the acid solution is selected from one or more of solutions of nitric acid, acetic acid, hydrochloric acid, phosphoric acid, and sulfuric acid.
10. The method according to claim 8 or 9, wherein the unmodified composite oxide AMn in which y and z are both 02O5Mixing metal salt of A and metal salt of Mn in a molar ratio of A to Mn of 1:1.8 to 1:2.2, and performing sol-gel method orCoprecipitation method.
11. Use of the modified composite oxide catalyst according to any one of claims 1 to 7 for catalytic purification of VOCs or NO or for synergistic purification removal of both VOCs and NO.
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| CN114768794B (en) * | 2022-04-27 | 2024-03-15 | 华南理工大学 | Composite manganese oxide catalyst for synchronously removing VOCs and NOx in medium-low temperature flue gas, and preparation method and application thereof |
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